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Title: Excitonic emissions and above-band-gap luminescence in the single-crystal perovskite semiconductors CsPbB r 3 and CsPbC l 3

Journal Article · · Physical Review. B, Condensed Matter and Materials Physics
 [1];  [1];  [2];  [3];  [1];  [1];  [2];  [3];  [1]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Material Science and Engineering
  2. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Physics and Astronomy

The ternary compounds CsPbX3 (X = Br or Cl) have perovskite structures that are being considered for optical and electronic applications such as lasing and gamma-ray detection. An above-band-gap excitonic photoluminescence (PL) band is seen in both CsPbX3 compounds. An excitonic emission peak centered at 2.98 eV, ~0.1 eV above the room-temperature band gap, is observed for CsPbCl3. The thermal quenching of the excitonic luminescence is well described by a two-step quenching model, yielding activation energies of 0.057 and 0.0076 eV for high- and low-temperature regimes, respectively. CsPbBr3 exhibits bound excitonic luminescence peaks located at 2.29 and 2.33 eV that are attributed to recombination involving Br vacancy centers. Activation energies for thermal quenching of the excitonic luminescence of 0.017 and 0.0007 eV were calculated for CsPbBr3. Temperature-dependent PL experiments reveal unexpected blueshifts for all excitonic emission peaks in CsPbX3 compounds. A phonon-assisted step-up process leads to the blueshift in CsPbBr3 emission, while there is a contribution from band-gap widening in CsPbCl3. Finally, the absence of significant deep level defect luminescence in these compounds makes them attractive candidates for high-resolution, room-temperature radiation detection.

Research Organization:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
NA0002522; AC02-06CH11357
OSTI ID:
1494838
Alternate ID(s):
OSTI ID: 1234041
Journal Information:
Physical Review. B, Condensed Matter and Materials Physics, Vol. 92, Issue 23; ISSN 1098-0121
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 235 works
Citation information provided by
Web of Science

References (75)

Generalized Gradient Approximation Made Simple journal October 1996
The Renaissance of Halide Perovskites and Their Evolution as Emerging Semiconductors journal September 2015
Projector augmented-wave method journal December 1994
Hybrid functionals based on a screened Coulomb potential journal May 2003
Combined effects of screening and band gap renormalization on the energy of optical transitions in ZnO and GaN journal November 2000
WinGX and ORTEP for Windows : an update journal July 2012
All-solid-state dye-sensitized solar cells with high efficiency journal May 2012
Luminescence of CsPbCl3 Nanocrystals Dispersed in a CsCl Crystal under High-Energy Excitation journal May 2001
Evidence for the direct population of solid-state bands by non-bonding electron pairs in compounds of the type CsM II X3(M II = Ge, Sn, Pb; X = Cl, Br, I) journal January 1995
Excitation intensity and temperature-dependent photoluminescence and optical absorption in Tl4Ga3InSe8 layered crystals journal August 2006
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells journal May 2009
Cesium-trihalogen-plumbates a new class of ionic semiconductors journal January 1979
Electrical conduction and phase transitions in CsPbCl3 journal September 1971
Linear Network Model of Gene Regulation for the Yeast Cell Cycle journal March 2004
Interface engineering of highly efficient perovskite solar cells journal July 2014
High-resolution studies of cubic perovskites by elastic neutron diffraction: CsPbCl 3 journal December 1979
Structural Phase Transitions in CsPbBr 3 journal November 1974
Radiative recombination via intrinsic defects in CuxGaySe2 journal April 2001
Excitons in CsPbX3 (X=Cl, Br, I) ternary nanocrystallites in thin film matrices journal December 2001
Mesoscopic CH3NH3PbI3/TiO2 Heterojunction Solar Cells journal October 2012
High intensity photoluminescence of microcrystalline CsPbBr3 films: Evidence for enhanced stimulated emission at room temperature journal January 2007
Bound excitons and resonant Raman scattering in Cd x Zn 1 − x Te ( 0.9 ≤ x ≤ 1 ) journal December 1983
Luminescence Spectroscopy of Semiconductors book February 2012
Temperature and Excitation Power Dependences of the Photoluminescencein CdMnTe Crystals journal May 2011
Crystal Growth of the Perovskite Semiconductor CsPbBr 3 : A New Material for High-Energy Radiation Detection journal June 2013
Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs journal December 2008
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] journal June 2006
Does the low-temperature Arrhenius plot of the photoluminescence intensity in CdTe point towards an erroneous activation energy? journal February 1997
Ab initiomolecular dynamics for liquid metals journal January 1993
Lead bromide and ternary alkali lead bromide single crystals — growth and emission properties journal August 1996
Polarization Phenomena in TlBr Detectors journal August 2009
Crystal Structure and Photoconductivity of Cæsium Plumbohalides journal November 1958
Photoluminescence and stimulated emission from microcrystalline Cs Pb Cl 3 films prepared by amorphous-to-crystalline transformation journal November 2004
Identification of the symmetry of phonon modes in CsPbCl3 in phase IV by Raman and resonance-Raman scattering journal December 1997
Luminescence of CsPbBr3-like quantum dots in CsBr single crystals journal October 1999
Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals journal January 2015
Phase transitions in ABX3 type halides journal March 1971
Low-energy excitation in CsPbX3 (X=Cl, Br) journal December 2002
Partial recovery of the fatigued photoluminescence in germanium sulfide glass journal June 2003
New Evidence for Defect Creation by High Optical Excitation in Glow Discharge Amorphous Silicon journal July 1980
Phase Transitions in CsPbCl 3 journal December 1971
Crystal Growth of Tl 4 CdI 6 : A Wide Band Gap Semiconductor for Hard Radiation Detection journal March 2014
Optical properties of Zn-terminated ZnO bulk journal February 2004
Shallow halogen vacancies in halide optoelectronic materials journal November 2014
Thermal Dissociation of Excitons Bounds to Neutral Acceptors in High-Purity GaAs journal November 1971
Strongly Enhanced Free-Exciton Luminescence in Microcrystalline CsPbBr 3 Films journal July 2003
Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9% journal August 2012
Structure validation in chemical crystallography journal January 2009
Free-to-bound recombination in near stoichiometric Cu 2 ZnSnS 4 single crystals journal July 2012
Ionic conductivity of CsPbCl3 and CsPbBr3 journal January 1987
A short history of SHELX journal December 2007
Temperature dependence of the photoinduced fatigue-recovery phenomena of photoluminescence under prolonged irradiation in GeS2 chalcogenide glass journal March 2008
Unusual defect physics in CH 3 NH 3 PbI 3 perovskite solar cell absorber journal February 2014
Temperature dependence of band gaps in Si and Ge journal February 1985
First principle study of the structural and optoelectronic properties of cubic perovskites CsPbM3 (M=Cl, Br, I) journal September 2011
Ionic conduction of the perovskite-type halides journal November 1983
Time-dependent photoluminescence fatigue-recovery phenomena in germanium sulfide glasses journal June 2013
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Heavy metal ternary halides for room-temperature x-ray and gamma-ray detection conference September 2013
Further Contribution to the Theory of the Line-Shape of the Exciton Absorption Band journal January 1962
Reinterpretation of degradation kinetics of amorphous silicon journal March 1989
First-principles calculations for point defects in solids journal March 2014
Photoluminescence Associated with Multivalley Resonant Impurity States above the Fundamental Band Edge: N Isoelectronic Traps in Ga As 1 − x P x journal July 1971
A neutron diffraction study of anharmonic thermal vibrations in cubic CsPb X 3 journal January 1980
Excitation-power dependence of the near-band-edge photoluminescence of semiconductors journal April 1992
Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites journal October 2012
Photoluminescence from the nitrogen-perturbed above-bandgap states in dilute GaAs1−xNx alloys: A microphotoluminescence study journal May 2006
Intrinsic point defects in aluminum antimonide journal April 2008
Temperature-dependent excitonic photoluminescence of hybrid organometal halide perovskite films journal January 2014
Neutron Diffraction Study of the Structure of Cubic CsPbBr 3 journal July 1979
Excitons versus free charges in organo-lead tri-halide perovskites journal April 2014
Excitation Intensity and Temperature-Dependent Photoluminescence and Optical Absorption in Tl4Ga3InSe8 Layered Crystals. journal October 2006
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020
Polarization phenomena in TlBr detectors
  • Hitomi, Keitaro; Kikuchi, Yohei; Shoji, Tadayoshi
  • 2008 IEEE Nuclear Science Symposium and Medical Imaging conference (2008 NSS/MIC), 2008 IEEE Nuclear Science Symposium Conference Record https://doi.org/10.1109/nssmic.2008.4775149
conference October 2008
Intrinsic point defects in aluminum antimonide text January 2010

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Pathways toward high-performance inorganic perovskite solar cells: challenges and strategies journal January 2019
CsPbBr 3 interconnected microwire structure: temperature-related photoluminescence properties and its lasing action journal January 2019
Excitation-intensity dependence of shallow and deep-level photoluminescence transitions in semiconductors journal November 2019
The influence of electrode for electroluminescence devices based on all-inorganic halide perovskite CsPbBr 3 journal November 2019
Comparison of superstar CsPbBr 3 and classical LaPO 4 :Tb 3+ ,Ce 3+ green-emitting nanophosphors journal February 2019
Assessment of the exact-exchange-only Kohn-Sham method for the calculation of band structures for transition metal oxide and metal halide perovskites journal August 2019
Carrier recombination mechanism in CsPbB r 3 revealed by time-resolved photoluminescence spectroscopy journal December 2019
Alloy-Free Band Gap Tuning across the Visible Spectrum journal June 2019
Impact of organic molecule rotation on the optoelectronic properties of hybrid halide perovskites journal December 2019
Frequency upconverted amplified spontaneous emission and lasing from inorganic perovskite under simultaneous six-photon absorption journal January 2018
Long-living nonlinear behavior in CsPbBr3 carrier recombination dynamics journal April 2019
Materials Discovery of Stable and Nontoxic Halide Perovskite Materials for High‐Efficiency Solar Cells journal April 2019
Inorganic and Layered Perovskites for Optoelectronic Devices journal September 2018
Halide-Perovskite Resonant Nanophotonics journal August 2018
On the structure, synthesis, and characterization of ultrafast blue-emitting CsPbBr 3 nanoplatelets journal January 2019
Coherent exciton-phonon coupling in perovskite semiconductor nanocrystals studied by two-dimensional electronic spectroscopy journal December 2019
Nonempirical hybrid functionals for band gaps of inorganic metal-halide perovskites journal December 2019
Halide-Perovskite Resonant Nanophotonics preprint January 2018
Materials Discovery of Stable and Nontoxic Halide Perovskite Materials for High-Efficiency Solar Cells text January 2019

Figures / Tables (14)